TW201300957A - Positive photosensitive siloxane composition - Google Patents

Abstract

The object of the present invention is to provide a positive photosensitive siloxane composition, which can form patterns having high resolution, high heat-resistance, and high transparency, and also can reduce pattern deficiencies which is due to re-adhesion of insoluble remainders, such as developing residues, dissolution residues, and others when the pattern forms. SOLUTION: The positive photosensitive siloxane composition contains (I) at least 3 or more kinds of polysiloxane, which have different solution rate in tetramethylammonium hydroxide water solution, (II) diazonaphthoquinone, and (III) solvent. The positive photosensitive siloxane composition is characterized by comprising at least 1 kind of the following polysiloxane (Ia), at least 1 kind of the following polysiloxane (Ib), and at least 1 kind of the following polysiloxane (Ic). (A)Polysiloxane (Ia) A polysiloxane prepared by hydrolysis-condensation existing acidic or basic catalyst of a silane compound, which is presented by general formula (1), the film of the polysiloxane after pre-baking is soluble in 5 mass% of tetramethylammonium hydroxide water solution, and the solution rate is less than or equal to 1, 000 Å /sec. R1nSi(OR2)4-n (In the formula, R1 represents a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms, wherein optional methylene can be substituted by oxygen. n is 0 or 1. R2 represents an alkyl group having 1 to 5 carbon atoms.) (B)Polysiloxane (Ib) A polysiloxane prepared by hydrolysis-condensation existing acidic or basic catalyst of a silane compound, which is presented by the general formula (1), the film of the polysiloxane after pre-baking is soluble in 2.38 mass% of tetramethylammonium hydroxide water solution, and the solution rate is less than or equal to 4, 000 Å /sec. (C)Polysiloxane (Ic) A polysiloxane prepared by hydrolysis-condensation existing acidic or basic catalyst of a silane compound, which is presented by the general formula (1), the film of the polysiloxane after pre-baking is soluble in 2.38 mass% of tetramethylammonium hydroxide water solution, and the solution rate is more than or equal to 200 Å /sec, and less than or equal to 3, 000 Å /sec.

Description

Positive photosensitive siloxane composition

The present invention relates to a positive photosensitive siloxane composition. More specifically, the present invention relates to a pattern which is optically transparent, resistant to high temperatures, high in chemical resistance and environmental resistance, and which can reduce developmental residues or dissolve residual or poorly soluble substances during development. A positive photosensitive siloxane composition having a pattern defect caused by reattachment or the like, and the positive photosensitive siloxane composition is suitably used for a display such as a liquid crystal display element or an organic electroluminescence (EL) display element. a flattening film for a thin film transistor (TFT) substrate or an interlayer insulating film of a semiconductor element used for a backplane, and a solid-state imaging element, an anti-reflection film, an anti-reflection plate, a filter, a high-brightness light-emitting diode, Various components such as touch panels, solar cells, and optical devices such as optical waveguides. Further, the present invention relates to a cured film formed from the positive photosensitive siloxane composition, and the above-mentioned element having the cured film.

In recent years, various proposals have been made to improve optical utilization efficiency or energy saving in optical components such as displays, light-emitting diodes, and solar cells. For example, in a liquid crystal display, a method in which a transparent flattening film is formed on a TFT and a pixel electrode is formed on the planarizing film to increase an aperture ratio of a display device is known (see Patent Document 1). In terms of the configuration of the organic EL device, it is also proposed to form a light-emitting layer by vapor deposition on a transparent pixel electrode formed on a substrate, and to extract light from the substrate side (bottom emission), or to borrow Forming a transparent image on a planarizing film formed on a TFT element Method for forming a light-emitting layer and a light-emitting layer thereon, and removing light from the light-emitting layer from the opposite side of the TFT element (top emission), and improving the aperture ratio in the same manner as the liquid crystal display (refer to the patent) Literature 2).

Further, with the high resolution, large size, high image quality, and 3D display of the display, signal delay on the wiring becomes a problem. Although the input signal to the TFT is shortened by the drawing conversion speed (frame frequency) of the image data, the wiring width expansion adopted to reduce the wiring resistance will be required from the viewpoint of high resolution. Limited. Therefore, it is proposed to solve the signal delay problem by increasing the wiring thickness (see Non-Patent Document 1).

A material obtained by combining an acrylic resin and a bismuth azide compound is known as a material of the flattening film for a TFT substrate (see Patent Documents 3 and 4). However, these materials do not rapidly deteriorate in material properties at a high temperature of 200 ° C or higher, but slowly decompose at 230 ° C or higher, and there is a so-called "transparent film" as the film thickness decreases and the substrate is treated at a high temperature. Coloring, light transmittance is reduced." In particular, a method of forming a film at a high temperature using a device such as PE-CDV on the transparent film material cannot be used. Further, in the case of the organic EL element, since the decomposition product adversely affects the luminous efficiency and the lifetime of the organic EL element, it is not preferable as an optimum material in use. Further, in general, an acrylic material to which heat resistance is imparted has a high dielectric constant. Therefore, as the parasitic capacitance caused by the insulating film is increased, the power consumption is increased, and the quality of the image quality is caused by the delay of the driving signal of the liquid crystal element. Even an insulating material having a large dielectric constant can reduce the capacity by, for example, increasing the film thickness, but It is generally difficult to form a uniform thick film, and the amount of material used is also increased, which is not preferable.

For materials having high heat resistance and high transparency, polyoxyalkylenes, especially silsesquioxane, are known. The sesquiterpene is a polymer containing a trifunctional fluorinated structural unit RSi (O _1.5 ), which is chemically related to inorganic vermiculite (SiO ₂ ) and organic polyfluorene (R ₂ SiO). The existence between them is only soluble in an organic solvent, and the cured product exhibits a specific compound having high heat resistance peculiar to inorganic vermiculite. As a component of the photosensitive composition, the polyoxyalkylene must be soluble in a developing solution such as an aqueous solution of tetramethylammonium hydroxide. Therefore, there is proposed a photosensitive composition comprising: a sesquisesquioxane compound obtained by imparting an acryl group to a specific cage type heptacosane, and an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound, an olefin An acrylic copolymer obtained by copolymerizing an unsaturated compound and bismuth diazide (see Patent Document 5). However, in the photosensitive composition produced by such a complicated system, since the content of the organic compound is high, the organic compound other than the polyoxane causes thermal deterioration, so that the heat resistance of the cured product is insufficient, and discoloration or decomposition gas cannot be ignored. The problem.

In the case of a photosensitive composition comprising polyoxyalkylene oxide and bismuth diazide, for example, a polyoxyalkylene which is insoluble in a developing liquid and a polyoxyalkylene system which is soluble in a developing liquid, and a double stack are proposed. By using a photosensitive composition in which yttrium nitride is combined, it is possible to prevent a pattern such as a hole or a line which is obtained after image development during heat curing from flowing, and the "pattern" which is lowered in resolution is loose (refer to Patent Document 6). ). However, if a polyoxyalkylene which is insoluble in the developing solution is used, the dissolved residue or the insoluble matter dissolved after the image is reattached. The cause of the occurrence of a pattern defect.

In order to maintain the solubility of the developing solution in addition to the stanol group, a method of thiolation of a part of the phenyl group of the phenyl polyoxyalkylene has been proposed (refer to Patent Document 7), or has azide nitridation. A caged sesquioxanes compound having a fluorene structure (see Patent Document 8). Among these oxanes, even if the stanol group in the development is reacted, the problem of formation of an insoluble layer and dissolution of a residue can be reduced by having a stable developer liquid-soluble group. However, such a cured product of polyoxyalkylene is not resistant to a chemical solution such as a photoresist stripping solution, and its use can be limited.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 2933879

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-236839

[Patent Document 3] Japanese Patent No. 2961722

[Patent Document 4] Japanese Patent No. 3783512

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-119777

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2007-193318

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2010-43030

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2007-293160

[Non-patent literature]

[Non-Patent Document] IMID/IDMC/ASIA DISPLAY 2008 Digest(p.9-p.12)

Therefore, the present invention is based on the above-described circumstances, the purpose of which is In order to provide a high-resolution, high heat-resistance, high-transparency pattern, and to reduce pattern defects caused by re-attachment of insoluble matter such as development residue and dissolved residue during pattern formation. A siloxane composition.

Further, another object of the present invention is to provide a cured film such as a planarizing film for a TFT substrate or an interlayer insulating film formed of the positive photosensitive siloxane composition, and a liquid crystal display element and an organic EL including the cured film. Components such as display elements, solid-state imaging elements, anti-reflection films, anti-reflection plates, filters, high-brightness light-emitting diodes, touch panels, solar cells, optical waveguides, and the like, or semiconductor elements.

As a result of intensive review by the present inventors, it has been found that in a positive photosensitive siloxane having a polyoxy siloxane, a diazonaphthoquinone derivative, and a solvent, it is used in an aqueous solution of tetramethylammonium hydroxide. At least three kinds of polyoxyalkylenes having different dissolution rates are used as the polyoxyalkylene to reduce pattern defects caused by re-adhesion of poorly soluble substances such as development residues or dissolved residues, and can be formed into high sensitivity and have A high-resolution, high residual film cured film, and the formed film is optically transparent, resistant to high temperatures, and has high drug resistance and environmental resistance; based on this knowledge, the present invention has been completed.

That is, the present invention relates to a positive photosensitive siloxane composition as shown below.

(1) A positive photosensitive siloxane composition comprising a (I) polyoxy siloxane, a (II) diazonaphthoquinone derivative, and a (III) solvent positive photosensitive siloxane composition , The polyoxyalkylene oxide (I) comprises at least one of the following polyoxyalkylene oxides (Ia), at least one of the following polyoxyalkylene oxides (Ib), and the following polyoxyalkylene oxide (Ic) At least one of; (A) polyoxyalkylene (Ia)

The decane compound represented by the formula (1) is obtained by hydrolysis and condensation in the presence of an acidic or basic catalyst, and the film after prebaking is 5% by weight of tetramethylammonium hydroxide (hereinafter referred to as "5% TMAH". ") a polyoxane having a dissolution rate of 1,000 Å/sec or less; R ¹ _n Si(OR ² ) _4-n (wherein R ¹ represents an arbitrary methylene group which can be replaced by oxygen) a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms and optionally hydrogen replaced with fluorine; n is 0 or 1; R ² represents a carbon number of 1 to 5 (alkyl); (B) polyoxyalkylene (Ib)

The decane compound of the formula (1) is hydrolyzed and condensed in the presence of an acidic or basic catalyst, and the film after prebaking is 2.38 wt% tetramethylammonium hydroxide (hereinafter referred to as "2.38% TMAH"). a polyoxane having a dissolution rate of 4,000 Å/sec or more in an aqueous solution; (C) polyoxyalkylene (Ic)

The decane compound of the formula (1) is hydrolyzed and condensed in the presence of an acidic or basic catalyst, and the film after prebaking has a dissolution rate of 200 Å/sec in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. Polyoxane above 3000 Å / sec.

(2) The positive photosensitive siloxane composition according to the above (1), wherein the polyoxy siloxane (Ia) is obtained by hydrolyzing and condensing the decane compound in the presence of a basic catalyst. .

(3) The positive photosensitive siloxane composition according to (1) or (2) above, wherein the total weight of the polyoxyalkylene (Ia) and (Ib), and the polyoxyalkylene (Ic) The weight ratio is from 95/5 to 50/50.

(4) The positive photosensitive siloxane composition according to any one of (1) to (3) above, wherein the weight ratio of the polyoxyalkylene (Ia) to (Ib) is from 30/70 to 70/30.

(5) The positive photosensitive siloxane composition according to any one of the above (1), wherein the polyoxyalkylene (I) contains 5 mole% to 30% by mole of a decane compound. The decane compound is n = 0 among the decane compounds of the formula (1) constituting the polyoxyalkylene.

(6) The positive photosensitive siloxane composition according to any one of (1) to (5) above, wherein at least one of the polyoxyalkylenes (Ia), (Ib) and (Ic) In the decane compound of the formula (1) constituting the polyoxyalkylene oxide, the decane compound represented by the methyl group of R ¹ is an average of 20 mol% to 80 mol%.

(7) The positive photosensitive siloxane composition according to the above (6), wherein the polyoxane (I) is a decane compound of the formula (1) constituting the polyoxyalkylene The decane compound in which R ¹ is a methyl group accounts for an average of 20 mol% to 80 mol%.

(8) A cured film comprising the positive photosensitive siloxane composition according to any one of the above (1) to (7).

(9) An element comprising the cured film according to (8) above.

The positive photosensitive siloxane composition of the present invention has high sensitivity and high resolution, and the obtained cured film has heat resistance, transparency, and residual film. It is excellent in the rate, and can reduce pattern defects caused by re-adhesion of a hard-to-dissolve such as a development residue or a dissolved residue during development. In addition, since it is excellent in flatness and electric insulating properties, it is suitably used for a flat film for a thin film transistor (TFT) substrate or an interlayer insulating film for a semiconductor element used for a substrate such as a liquid crystal display device or an organic EL display device. And various film forming materials such as solid-state imaging elements, anti-reflection films, anti-reflection plates, filters, high-brightness light-emitting diodes, touch panels, solar cells, and the like, or transparent protective films. It is also applicable to optical devices such as optical waveguides.

Hereinafter, the positive photosensitive siloxane composition of the present invention will be described in more detail.

As described above, the positive photosensitive siloxane composition of the present invention contains at least three kinds of polyoxaxane and diazonaphthoquinone derivatives having different dissolution rates in an aqueous solution of tetramethylammonium hydroxide, and Solvents are characteristic. Hereinafter, the polyoxyalkylene oxide, the diazonaphthoquinone derivative, and the solvent used in the positive photosensitive siloxane composition of the present invention will be described in detail in order.

(I) polyoxyalkylene oxide

First, the characteristics of the polyoxyalkylene used in the present invention will be described.

The polyoxyalkylene used in the present invention is at least three kinds of polyoxoxanes (Ia), (Ib) and (Ic) having different dissolution rates in an aqueous solution of tetramethylammonium hydroxide (TMAH) as described above. .

Furthermore, in the case of a diazonaphthoquinone derivative as a dissolution inhibitor, 2.38% TMAH aqueous solution is used as a developing solution to form a photosensitive siloxane composition. If the dissolution rate of polyoxy siloxane in 2.38% TMAH is 100 Å/sec or more, it can be practically formed by exposure-development. Positive pattern. However, such a polyoxyalkylene usually undergoes a "pattern" loose during heat hardening.

The "pattern" is loose and can be prevented by using a polyoxyalkylene having a low dissolution rate in the developing solution. However, as described in Patent Document 6, when the molecular weight of polyoxymethane is increased, it becomes difficult to dissolve in a 2.38% TMAH aqueous solution of a developing solution, and the dissolved residue after development may cause a decrease in resolution, or Low sensitivity, and even cause problems such as pattern defects after development. Examples of other polyoxyalkylene having a low dissolution rate include a low molecular weight substance such as a caged sesquioxanes, a structure containing a stanol group, and the like. The appropriate dissolution rate in the 2.38% TMAH aqueous solution can be adjusted by mixing the polyoxane having a low dissolution rate with the polyoxane having a relatively high dissolution rate.

The present invention is characterized in that, regardless of the structure of the polyoxyalkylene, the polyoxane having a low dissolution rate in a 2.38% TMAH aqueous solution is combined with a polyoxane having a higher dissolution rate in a 2.38% TMAH aqueous solution. Further, polysiloxanes having a dissolution rate between the dissolution rates of the polyoxyalkylenes are mixed, and at least three polyoxoxanes are used.

Thus, in the present invention, polyfluorene oxide (Ia) is used as the aforementioned polyoxane having a low dissolution rate in a 2.38% aqueous solution of TMAH, which is in a 2.38% aqueous solution of TMAH. In order to be insoluble, a polyoxane obtained by hydrolyzing and condensing a decane compound represented by the formula (1) R ¹ _n Si(OR ² ) _4-n in the presence of an acidic or basic catalyst, The baked film was soluble in a 5% TMAH aqueous solution and had a dissolution rate of 1,000 Å/sec or less. In the case of such a polyoxane (Ia), one type may be used alone or two or more types may be used in combination.

On the other hand, polyoxyalkylene (Ib) is used as a polyoxane having a higher dissolution rate in a 2.38% aqueous solution of TMAH, which is obtained by using a decane compound of the formula (1). And obtained by hydrolysis and condensation in the presence of an acidic or basic catalyst, and the pre-baked film is dissolved in a 2.38% TMAH aqueous solution at a rate of 4,000 Å/sec or more of polyfluorene oxide. The oxane (Ib) can be used in combination with the aforementioned polyoxyalkylene (Ia). In the case of the polyoxyalkylene (Ib), one type may be used alone or two or more types may be used in combination.

Further, in the present invention, in addition to the polyoxyalkylene oxides (Ia) and (Ib), at least one polyoxane (Ic) is used, and the polyoxyalkylene (Ic) is used by using the aforementioned a decane compound of the formula (1), which is obtained by hydrolysis and condensation in the presence of an acidic or basic catalyst, and the dissolution rate of the film after prebaking in a 2.38% aqueous solution of TMAH is in the polyoxane (Ia). Between the dissolution rate of polyoxyalkylene (Ib), that is, the dissolution rate in the 2.38% TMAH aqueous solution is 200 Å / sec or more and 3000 Å / sec or less.

Therefore, the dissolution rate of at least three or more kinds of polyoxane mixtures having different dissolution rates in the TMAH aqueous solution in the 2.38% TMAH aqueous solution can be made up of 2.38% TMAH aqueous solution as long as it is 100 to 1,000 Å/sec. A polyoxane composition of a developing solution. Therefore, the above-mentioned at least three kinds of polyoxyalkylene oxides, specifically, the amounts of polyoxyalkylene oxides (Ia), (Ib), and (Ic) are considered to be polysiloxanes (Ia) to be used. Under the solubility characteristics of Ib) and (Ic), the mixture is adjusted to The dissolution rate of the 2.38% TMAH aqueous solution can satisfy the above-mentioned amount of 100 to 1,000 Å/sec.

On the other hand, in the mixture of polyoxane (Ia), (Ib), and (Ic), if the content of the vermiculite structure of n=0 is increased, the crosslinking density is increased, and the "pattern" is loose. Can be eased. The polyoxyalkylene (Ia) has a heat release prevention effect of "pattern", but it contains a poorly soluble component, which is not preferable from the viewpoint of development residue. As described above, by increasing the content of the vermiculite structure, the heat looseness of the "pattern" can be alleviated, and the amount of the polyoxane (Ia) containing the poorly soluble component can be reduced, but if n = When the content of the meteorite structure of 0 is excessively increased, the reactivity of the polyoxyalkylene oxide becomes high, and insoluble components may be formed during development. From this point of view, in the polyoxane mixture, the content of the vermiculite structure of n = 0 in the general formula (1) is preferably from 5 mol% to 30 mol%. For example, in the case of polyoxyalkylene (Ia), the content of the vermiculite structure of n=0 is preferably 20 mol% or less, and in the case of polyoxyalkylene (Ib), 30 mol%. The following is preferable, and in the case of polyoxyalkylene (Ic), it is preferably 30 mol% or less.

When the pattern is formed using the positive photosensitive siloxane composition of the present invention, the positive photosensitive siloxane composition is applied onto a substrate to form a coating film, and after exposure, development is carried out. After the development, in order to form a hardened film, it is preferable to heat at a temperature of 200 ° C or higher, but the pattern after development at this time flows. In order to suppress such heat flow and maintain the pattern shape, the weight ratio of polyoxyalkylene (Ia) / (Ib) is preferably from 30/70 to 70/30. When the polyoxyalkylene (Ia) exceeds 70 parts by weight, the sensitivity is remarkably lowered and it becomes unpractical. Further, in order to eliminate the development residue, the total weight of the polyoxyalkylene (Ia) and (Ib) is preferably from 95/5 to 50/50 by weight of the polyoxyalkylene (Ic). When the ratio of the polyoxyalkylene (Ic) is 5 parts by weight or less, the development residue is not sufficiently prevented. On the other hand, when the amount is 50 parts by weight or more, the ratio of the polyoxane (Ia) in the polyoxane mixture is insufficient, and the problem of heat flow becomes remarkable.

Further, in the case of the polyoxyalkylene (Ia), a polyoxyalkylene synthesized by an alkaline catalyst is preferably used because it can form a photosensitive siloxane composition having a "pattern" loosening prevention effect.

The weight average molecular weight (Mw) of the mixture of polyoxyalkylene (Ia), (Ib) and (Ic) is preferably 5,000 or less, more preferably about 1,000 to 3,000. When the weight average molecular weight (Mw) of the mixture is less than 1,000, the "pattern" loosening prevention effect is small. On the other hand, when it is 5,000 or more, since the residue is dissolved during development, sufficient resolution cannot be obtained, and the sensitivity is also lowered. .

The polyoxyalkylenes (Ia), (Ib) and (Ic) used in the composition of the decane resin of the present invention can be obtained by using an organic solvent in the presence of a basic or acidic catalyst. The decane compound represented by the formula (1) is produced by hydrolysis and condensation.

The following are more specifically described for polyoxyalkylenes (Ia), (Ib) and (Ic), but the difference in dissolution rate, which is adjusted for the acid catalyst material, can be adjusted by the length of the reaction time, and The material of the catalyst can be adjusted by increasing or decreasing the amount of water added during the reaction; in addition to appropriately adjusting the reaction time or the amount of water, the polyoxane (Ia), (Ib) and (Ic) can be as follows Order, manufactured in the same way. Therefore, in the following description, in the case where it is not necessary to distinguish between polyoxane (Ia), (Ib) and (Ic), it may be simply referred to as "polyoxane".

Poly Silicon manufacturing alumoxane are necessary for the general formula _{^{(1) R 1 n Si (}} OR 2) 4-n of R ^1, a methylene group represents any of the available carbon atoms of oxygen replacement of 1 to 20 linear, branched a cyclic or cyclic alkyl group, or an aryl group having 6 to 20 carbon atoms and optionally hydrogen may be replaced by fluorine; and R ² represents an alkyl group having 1 to 5 carbon atoms. n is 0 or 1. Two or more kinds of the decane compounds of the above formula (1) may be used in combination.

In the general formula (1), as the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may be replaced by oxygen with respect to any methylene group of R ¹ , for example, a methyl group or an ethyl group may be mentioned. , n-propyl, isopropyl, tert-butyl, n-hexyl, n-decyl, trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, cyclohexyl Wait. Further, examples of the aryl group having 6 to 20 carbon atoms and any hydrogen may be replaced by fluorine include a phenyl group, a tolyl group, a naphthyl group and the like. Among these bases, it is easy to obtain from a raw material, and the film hardness is high after hardening, and a methyl group is a preferable base with high chemical resistance; Moreover, the hardening film is not improved from the solubility of the polyoxyalkylene in a solvent. In the case where cracks are easily formed, a phenyl group and a naphthyl group are preferred groups, and a methyl group is particularly preferred.

When a methyl group is used as R ¹ , if the content of the methyl group of R ^{1 in} the polyoxyalkylene (I) is small, the resistance to the photoresist stripping solution is poor, and conversely, if the content is too large, the rhodium alkane is used. The activity becomes high and becomes a cause of insoluble matter formation. Therefore, in the polyoxyalkylene (I), the ratio of the decane compound represented by the formula (1) wherein R ¹ is a methyl group is preferably from 20 mol% to 80 mol%. Further, in each of the polyoxyalkylene oxides (Ia), (Ib), and (Ic), in any one of these, R ¹ is a methyl group in the formula (1) for producing a polyoxyalkylene oxide. The ratio of the decane compound shown is preferably from 20 mol% to 80 mol%; about two polyoxoxanes selected from the group consisting of polyoxyalkylenes (Ia), (Ib) and (Ic) The mixture, at least one of the mixtures, wherein R ¹ is a ratio of the decane compound represented by a methyl group, is preferably from 20 mol% to 80 mol%. Further, it is more preferred that each of the polyoxyalkylene oxides (Ia), (Ib), and (Ic) is 20 mol% to 80 mol%.

And, R & lt Silane Compound ¹ in the general formula (1) to include the case where plural kinds of compounds, such plurality of compounds in R ^1, may each be identical or different. In the case where R ¹ is a methyl group-containing decane compound, it is preferred to use a decane compound in which R ¹ is a phenyl group as the other decane compound of the formula (1).

On the other hand, examples of the alkyl group having 1 to 5 carbon atoms of R ² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. R ² may be the same or different. When the decane compound of the formula (1) contains a plurality of compounds, R ^{2 of the} plurality of compounds may be the same or different.

Specific examples of n=1 in the decane compound represented by the above formula (1) include, for example, methyltrimethoxydecane, methyltriethoxydecane, and methyltriisopropoxydecane. , methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, n-propyl trimethoxy decane , n-propyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, decyl trimethoxy decane, benzene Trimethoxy decane, phenyl triethoxy decane, trifluoromethyl trimethoxy decane, trifluoromethyl triethoxy decane, 3,3,3-trifluoropropyltrimethoxydecane, naphthyl Trimethoxydecane, naphthyltriethoxydecane, naphthyltriisopropoxydecane, naphthyltri-n-butoxydecane, and the like. Among these, methyltrimethoxydecane, methyltriethoxy Decane, phenyltrimethoxydecane, and phenyltriethoxydecane are preferred compounds which are easy to obtain.

Further, specific examples of the decane compound having n = 0 among the decane compounds represented by the formula (1) include tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, and the like. Butoxy oxane and the like. Among them, tetramethoxy decane, tetraethoxy decane and the like are preferably highly reactive.

The polyoxyalkylene of the present invention is produced by hydrolyzing and condensing a decane compound represented by the above formula (1) in the presence of a basic or acidic catalyst.

At the time of manufacture, a mixed solution of a decane compound represented by the formula (1) is dropped into a mixed solution of an organic solvent, a catalyst, and water to carry out hydrolysis and condensation reaction, and if necessary, by neutralization or washing. The purification is carried out by concentration, removal of reaction by-products, change of concentration, replacement with a desired organic solvent, and the like.

The organic solvent used in the reaction may be used singly or in combination of plural kinds. Specific examples of the solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene; ether solvents such as diethyl ether and tetrahydrofuran; and ester solvents such as ethyl acetate; methanol, ethanol, and isopropyl alcohol. An alcohol solvent such as an alcohol or a butanol; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; the amount used is 0.1 to 10 times by weight of the mixture of the decane compounds, and 0.5 to 2 times. Weight times are preferred.

The dropping solution of the decane compound and the reaction temperature are 0 to 200 ° C, and preferably 10 to 60 ° C, and the dropping temperature and the reaction temperature may be the same or may be different. The reaction time varies depending on the substituent R ^{2 of the} decane compound structure represented by the above formula (1), but is usually from several tens of minutes to several tens of hours, and various conditions of hydrolysis and condensation reaction are considered in terms of reaction scale and reaction vessel. The physical properties suitable for the intended use can be obtained by setting, for example, the amount of the catalyst, the reaction temperature, the reaction time, and the like.

Examples of the basic catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, and trisole. An organic base such as ethanolamine, diethanolamine or an alkoxy decane having an amine group; an inorganic base such as sodium hydroxide or potassium hydroxide; an anion exchange resin or tetrabutylammonium hydroxide, tetraethylammonium hydroxide or tetramethyl hydroxide A quaternary ammonium salt such as a quaternary ammonium salt. The amount of the catalyst is preferably 0.0001 to 10 mol times which is equivalent to the decane compound.

In the case of using an alkaline catalyst, the degree of hydrolysis can be adjusted by the amount of water added. Although the amount of water added varies depending on the kind and amount of the decane to be used, in general, in the case of synthesizing polyoxyalkylene (Ia), hydrolysis with respect to the decane compound represented by the general formula (1) Alkoxy group, water should be reacted at a ratio of 0.01 to 10 moles (preferably 0.5 to 0.9 moles); in the case of synthesis of polyoxyalkylene (Ib), relative to the formula ( 1) The hydrolyzable alkoxy group of the decane compound shown is preferably reacted in a ratio of 0.01 to 10 moles (preferably 1.4 to 2.0 moles); in the synthesis of polyoxyalkylene (Ic) In the case of the hydrolyzable alkoxy group of the decane compound represented by the formula (1), it is preferred to carry out the reaction at a ratio of 0.01 to 10 moles (preferably 0.9 to 1.4 moles).

After the reaction is completed, an acidic compound can be used as a neutralizing agent to neutralize the reaction solution to be neutral or acidic. Examples of the acidic compound include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, and hydrofluoric acid; monocarboxylic acids such as acetic acid, trifluoroacetic acid, formic acid, lactic acid, and acrylic acid; oxalic acid, maleic acid, and succinic acid; Polycarboxylic acid such as citric acid and its anhydride, An organic acid such as a sulfonic acid such as toluenesulfonic acid or methanesulfonic acid; or a cation exchange resin.

The amount of the neutralizing agent is appropriately selected depending on the pH of the reaction liquid containing the polyoxyalkylene oxide, but it is preferably 0.5 to 1.5 moles, more preferably 1 to 1.1 moles, relative to the alkaline catalyst. good.

On the other hand, examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof, and an ion exchange resin. The amount of the catalyst added varies depending on the strength of the acid, but it is preferably 0.0001 to 10 mol times based on the mixture of the decane compound.

In the case of using an acidic catalyst, the type and amount of decane used vary, but in general, the degree of hydrolysis can be adjusted by stirring time. In general, in the case of synthesizing polyoxyalkylene (Ia), the stirring time is preferably from 8 to 12 hours; in the case of synthesizing polyoxyalkylene (Ib), the stirring time is preferably from 1 to 5 hours; In the case of synthesizing polyoxyalkylene (Ic), the stirring time is preferably from 5 to 12 hours.

After the completion of the reaction, the reaction solution may be neutralized in the same manner as in the case of using an alkaline catalyst. In the case of using an acidic catalyst, a basic compound is used as a neutralizing agent, and in the case of neutralizing the basic compound used, triethylamine, tripropylamine, tributylamine, and tripentylamine are mentioned. , an organic base such as trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine or diethanolamine; an inorganic base such as sodium hydroxide or potassium hydroxide; an anion exchange resin; or tetrabutyl hydroxide A quaternary ammonium salt such as ammonium, tetraethylammonium hydroxide or tetramethylammonium hydroxide. The amount of the neutralizing agent is preferably 0.5 to 15 moles per mole of the acidic catalyst, and more preferably 1 to 1.1 moles.

After neutralization, the neutralizing solution is washed and refined, depending on the necessity of coating film or storage stability. In terms of conditions, a hydrophobic organic solvent and optionally added water are added to the neutralizing solution to mix and contact, and at least the polyoxyalkylene oxide is dissolved in the hydrophobic organic solvent. As the hydrophobic organic solvent, a compound which can dissolve the polyoxyalkylene and is not mixed with water is used. By not mixing with water, it means that if water and a hydrophobic organic solvent are thoroughly mixed and allowed to stand, the aqueous layer and the organic layer are separated.

Examples of the preferred hydrophobic organic solvent include ether solvents such as diethyl ether; ester solvents such as ethyl acetate; alcohol solvents such as butanol; and ketones such as methyl ethyl ketone and methyl isobutyl ketone. A solvent; an aromatic solvent such as toluene or xylene. The above-mentioned hydrophobic organic solvent may be the same as the reaction solvent used in the reaction, or may be used in combination of two or more kinds. By washing, the alkaline catalyst, the acid catalyst, the neutralizing agent, and the like, which have been used up to now, together with the alcohol or water which is the by-product of the reaction, are contained in the water layer, but substantially The upper layer is removed from the organic layer, but the number of times of washing can be appropriately set depending on characteristics such as coating film characteristics and storage stability required.

The temperature for washing is not particularly limited, but it is preferably from 0 ° C to 70 ° C, more preferably from 10 ° C to 60 ° C. Further, the temperature at which the aqueous layer is separated from the organic layer is not particularly limited. However, it is preferably from 0 ° C to 70 ° C, and more preferably from 10 ° C to 60 ° C from the viewpoint of shortening the liquid separation time.

After washing, a solution containing a hydrophobic solvent for washing with polyoxyalkylene can be used as it is, but the solvent or the remaining side reaction product (ie, alcohol or water) can be removed by concentration, depending on the purpose. Change the concentration or replace it with another solvent. Concentration can be carried out under normal pressure (atmospheric pressure) or reduced pressure The degree of enrichment can be arbitrarily changed by controlling the amount of distillation. The temperature at the time of concentration is 30 ° C to 150 ° C, preferably 40 ° C to 100 ° C. Further, in order to form a target solvent composition, the solvent may be replaced by adding a desired solvent at appropriate time and further concentrating.

By the above manner, the polyoxyalkylene oxides (Ia), (Ib) and (Ic) used in the composition of the decane resin of the present invention can be produced, and by mixing these, a polydecane can be obtained. (I).

Furthermore, although a 2.38% aqueous solution of TMAH is generally used as a developing solution, the dissolution rates of polyoxyalkylenes (Ib), (Ic) and polyoxyalkylene (I) are set to the above ranges, but it is assumed that These different aqueous solutions of TMAH concentration are used as the developing solution, and the dissolution rates of polyoxyalkylene (Ib), (Ic) and polyoxyalkylene (I) are as long as the dissolution rate in the developing solution used. The same effect as in the present invention can be obtained by adjusting the range of the dissolution rate in the case where the above-mentioned 2.38% TMAH aqueous solution is used as the developing solution. Further, the same applies to the case where an inorganic alkaline aqueous solution such as sodium hydroxide other than TMAH is used as the developing liquid.

(Measurement and calculation method of alkaline dissolution rate (ADR))

The dissolution rate of polyoxyalkylene (Ia), (Ib) and (Ic) or a mixture of these in aqueous TMAH solution was measured and calculated in the following manner.

That is, first, the polyoxyalkylene was diluted and dissolved so as to be about 35% by weight in propylene glycol monomethyl ether acetate (PGMEA). This solution was spin-coated on a tantalum wafer so that the dried film thickness became a thickness of about 2 μm, and then the solvent was further removed by heating on a hot plate at 100 ° C for 60 seconds. The film thickness of the coating film was measured by a ellipsometer (manufactured by Woollam Co., Ltd.). Then, there will be twins with the film The circle was immersed in the following developer at room temperature (25 ° C): polyoxyalkylene (Ia) was immersed in 5% TMAH aqueous solution, polyoxyalkylene (Ib) and (Ic), and polyoxyalkylene The mixture of (Ia) and (Ib) and (Ic) was immersed in a 2.38% TMAH aqueous solution, and the time until the film disappeared was measured. The dissolution rate was determined by dividing the initial film thickness by the time until the film disappeared. When the dissolution rate was remarkably slow, the film thickness after immersion for a certain period of time was measured, and the amount of change in film thickness before and after immersion was divided by the immersion time to calculate the dissolution rate.

(II) Diazonaphthoquinone derivatives

The photosensitive azide composition containing a diazonaphthoquinone derivative of the present invention can form a positive form which is removed by development by making the exposed portion soluble in the alkaline developing solution. The diazonaphthoquinone derivative of the present invention is a compound in which a compound having a phenolic hydroxyl group is ester-bonded with naphthoquinonediazidesulfonic acid; although the structure is not particularly limited, the system has one or more phenolic properties. An ester compound formed by a compound of a hydroxyl group is preferred. As the naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid can be used. The 4-naphthoquinonediazide sulfonate compound is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. Further, the 5-naphthoquinonediazide sulfonate compound is suitable for exposure over a wide range of wavelengths because it has absorption over a wide range of wavelength regions. It is preferred to select a 4-naphthoquinonediazide sulfonate compound or a 5-naphthoquinonediazide sulfonate compound depending on the wavelength of exposure. A 4-naphthoquinonediazide sulfonate compound may also be used in combination with a 5-naphthoquinonediazide sulfonate compound.

The compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include the following compounds (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

The optimum amount of the diazonaphthoquinone derivative to be added, although the esterification ratio of the naphthoquinonediazidesulfonic acid, or the physical properties of the polysiloxane used, the required sensitivity, the exposed portion and the unexposed portion The solubility is different, but it is preferably 3 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of the polyoxyalkylenes (Ia), (Ib) and (Ic). When the amount of the diazonaphthoquinone derivative added is less than 3% by weight, the dissolution of the exposed portion and the unexposed portion is too low, and the actual photosensitivity is not obtained. Further, in order to further obtain a good dissolution ratio of the exposed portion and the unexposed portion, it is more preferably 8% by weight or more. On the other hand, in the case where the amount of the diazonaphthoquinone derivative is more than 20% by weight, the whitening of the coating film is caused by the deterioration of the compatibility between the polysiloxane and the bismuth subnitride compound. The decomposition of the bismuth diazide compound caused by the heat hardening causes the coloring to become remarkable, and the colorless transparency of the cured film is lowered. In addition, since the heat resistance of the diazonaphthoquinone derivative is inferior to that of polyoxymethane, when the amount of addition is increased, the electrical insulating property of the cured product during thermal decomposition is deteriorated or the gas is released, which is a subsequent step. problem. Further, the resistance of the cured product to the photoresist stripping solution such as monoethanolamine as a main component is lowered.

(III) solvent

The solvent may, for example, be an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether or ethylene glycol monobutyl ether; diethylene glycol II Diethylene glycol dialkyl ethers such as methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether Ethylene glycol alkyl ether acetate such as acid ester; propylene glycol monoether acetate acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; benzene, toluene Aromatic hydrocarbons such as xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexyl Alcohols such as alcohol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. These solvents may be used singly or in combination of two or more kinds, and the amount used may vary depending on the coating method and the film thickness after coating.

For example, in the case of spray coating, the ratio of the solvent in the photosensitive siloxane composition is 90% by weight or more, but in the case of slit coating used for a large substrate, the solvent is usually 60% by weight. The above is preferably 70% by weight or more. Positive photosensitive light of the present invention The properties of the siloxane composition do not vary greatly with the amount of solvent.

Further, in the positive photosensitive siloxane composition of the present invention, a surfactant may be contained as needed. The surfactant is added for the purpose of improving coating properties, developing properties, and the like. The surfactant which can be used in the present invention may, for example, be a nonionic surfactant, an anionic surfactant, an amphoteric surfactant or the like.

The above nonionic surfactant may, for example, be a polyoxyethylene ethyl ether, such as polyoxyethylidene ethyl ether, polyoxyethyl ether, polyoxyethyl ether Polyoxyethylene ethyl ethers such as ethers; or polyoxyethylene ethyl esters, polyoxyethyl esters; polyoxyethylene/polyoxypropyl propyl block polymers; Acetylene alcohol; acetylene glycol; polyacetylene oxide of acetylenic alcohol; acetylenic diol derivative such as polyethoxylate of acetylenic diol; fluorinated surfactant, such as Fluorad ( Product name, Sumitomo 3M Co., Ltd.), Magafac (trade name, manufactured by DIC Corporation), Sulfron (trade name, manufactured by Asahi Glass Co., Ltd.), or organic oxane surfactant, such as KP341 (trade name, Shin-Etsu Chemical Co., Ltd.) and so on. With respect to the aforementioned acetylenic diol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4- Octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol 2,5-Dimethyl-3-hexyne-2,5-diol, 2,5-dimethyl-2,5-hexanediol, and the like.

Further, examples of the anionic surfactant include an ammonium salt or an organic amine salt of an alkyl diphenyl ether disulfonic acid, an ammonium salt or an organic amine salt of an alkyl diphenyl ether sulfonic acid, and an alkylbenzene. Ammonium sulfonate or organic amine salt, polyoxygen An ammonium salt or an organic amine salt of an ethyl alkyl ether sulfate, an ammonium salt of an alkyl sulfate or an organic amine salt, or the like.

Further, examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl-imidazolium betaine, lauryl propyl hydroxysulfonyl betaine, and the like.

These surfactants may be used singly or in combination of two or more kinds, and the amount thereof is usually from 50 to 2,000 ppm, preferably from 100 to 1,000 ppm, based on the photosensitive siloxane composition of the present invention. .

Further, in the photosensitive siloxane composition of the present invention, a sensitizer may be added as needed. For the preferred sensitizer used in the positive photosensitive siloxane composition of the present invention, there are coumarin, ketocumarin and derivatives thereof, thiopyran Specific examples of the (thiopyrylium) salt and the acetophenone benzene include p-bis(o-methylstyryl)benzene and 7-dimethylamino-4-methylquinolinone-2. 7-Amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2-(p-dimethylaminostyryl)-pyridylmethyl Iodine, 7-diethylamino coumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6,-1H,4H-tetrahydro-8-methylquin And -<9,9a,1-gh>coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin , 7-Amino-4-trifluoromethylcoumarin, 2,3,5,6,-1H,4H-tetrahydroquine -<9,9a,1-gh>coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethyl Coumarin, 2,3,5,6,-1H,4H-tetrahydro-9-ethoxycarbonylquin -<9,9a,1-gh>coumarin, 3-(2'-N-methylbenzimidazolyl)-7-N,N-diethylamine coumarin, N-methyl -4-trifluoromethyl piperidine-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolylethyl iodide, 3-(2' -benzimidazolyl)-7-N,N-diethylamino coumarin, 3-(2'-benzothiazolyl)-7-N,N-diethylamino coumarin, and A sensitizing dye such as a pyrylium salt or a thiopyranium salt represented by the following chemical formula. By adding the sensitizing dye, it is possible to pattern using a low-cost light source such as a high-pressure mercury lamp (360 to 430 nm).

The coating film of the photosensitive siloxane component of the present invention can be formed by a general coating method, that is, dip coating, roll coating, bar coating, brush coating, spray coating, doctor blade coating, and flow coating. Previous photosensitive siloxane composition such as spin coating or slit coating Any method known in the coating method is carried out. Further, the substrate can be formed on a suitable substrate such as a ruthenium substrate, a glass substrate or a resin film. In the case where the substrate is a film, gravure coating may also be employed. A drying step of the coating film may be additionally provided as desired. For the coating film, it may be repeatedly applied one or two times or more to form a desired thickness.

After the coating film of the photosensitive siloxane composition of the present invention is formed, it is preferred to pre-bake (heat-treat) the coating film in order to dry the coating film and reduce the residual amount of the solvent. The prebaking step can be carried out usually at a temperature of 70 to 150 ° C, preferably 90 to 120 ° C. In the case of using a heating plate, 10 to 180 seconds is performed, preferably 30 to 90 seconds, and no In the case of a clean oven, it is carried out for 1 to 30 minutes.

A pattern forming method of the positive photosensitive siloxane composition of the present invention will be described. The desired pattern is obtained by forming a coating film of the positive photosensitive siloxane composition and pre-baking the coating film, and irradiating the coating film with a pattern. For such a light source, a lamp such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, or a laser diode, an LED, or the like can be used. For the irradiation light, ultraviolet rays such as g-line, h-line, and i-line can be usually used. In addition to ultra-fine processing such as semiconductors, in the case of patterning of several μm to several tens of μm, light of 360 to 430 nm (high-pressure mercury lamp) is generally used. Among them, in the case of a liquid crystal display device, light of 430 nm is often used. In such a case, it is advantageous to combine the sensitizing dyes in the photosensitive siloxane composition of the present invention as described above. The energy of the illuminating light varies depending on the light source or the initial film thickness, but is generally adjusted to 10 to 2000 mJ/cm ² , preferably 20 to 1000 mJ/cm ² . When the irradiation light energy is less than 10 mJ/cm ² , the composition cannot be sufficiently decomposed, and if it is higher than 2000 mJ/cm ² , the exposure becomes excessive, and halation may occur.

In order to perform illumination in a pattern, a general reticle can be used, and such a reticle is well known to those of ordinary skill in the art to which the present invention pertains. The environment at the time of irradiation is generally in the surrounding environment (in the atmosphere) or in a nitrogen atmosphere. Further, in the case where the film is formed in an all-round manner, it is sufficient to perform exposure after the entire coating. In the present invention, the pattern film also includes such a case where the film is formed integrally.

Further, as the developing liquid used for development, any developing liquid used in the development of the conventional photosensitive siloxane composition can be used. Examples of preferred imaging liquids include tetraalkylammonium hydroxide, choline, alkali metal hydroxide, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia water, An alkaline developing solution such as an aqueous solution of a basic compound such as an alkylamine, an alkanolamine or a heterocyclic amine, and a particularly preferred alkaline developing solution are tetramethylammonium hydroxide aqueous solutions. Further, in such an alkaline developing solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be further contained as needed. After development by an alkaline developing solution, water washing is usually carried out. Thereafter, in the case of using as a transparent film, bleaching exposure is preferred. By performing bleach exposure, the unreacted diazonaphthoquinone derivative remaining in the film can be photodecomposed to further improve the optical transparency of the film. For the method of bleach exposure, a UV-visible light exposure machine such as PLA can be used to fully expose about 100 to 2,000 mJ/cm ² (converted to an exposure amount of 365 nm).

After the development, the coating film can be hardened by heating the pattern film. As far as the heating conditions are concerned, as long as the coating film can be hardened, it can be any The temperature is usually 150 to 400 ° C, preferably 200 to 350 ° C. When it is 150 ° C or less, unreacted stanol groups remain, and sufficient chemical resistance cannot be exhibited. Moreover, the polarity of the stanol induces a high dielectric constant. Therefore, in the case of lowering the dielectric constant, it is preferred to harden it at 200 ° C or higher.

The crosslinked cured film thus obtained has heat resistance of 400 ° C or higher, and the light transmittance of the film is 95% or more, and the specific dielectric constant is also 4 or less, preferably 3.3 or less. Therefore, it has a light transmittance and a specific dielectric property which are not possessed by the acrylic material, and is suitable as a flat panel display (FPD) or the like, such as a flattening film or an interlayer insulating film or a transparent protective film of various elements described above, and the like. It is used as an interlayer insulating film for low temperature polysilicon, a buffer coating film for IC wafers, and the like. Further, the cured product may be used as an optical device material or the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by these examples and comparative examples.

<Synthesis Example>

First, a synthesis example of the polyoxyalkylene of the present invention is shown below. Furthermore, the following devices were used in the measurement.

GPC: HLC-8220GPC (manufactured by Tosoh Corporation)

Rotary coating machine: MS-A100 (manufactured by Mikasa Co., Ltd.)

<Synthesis Example 1 (Synthesis of Polyoxane (Ia-1): Synthesis of Base Catalyst)>

In a 2 L flask equipped with a stirrer, a thermometer, and a cooling tube, 36.5 g of a 25 wt% aqueous solution of tetramethylammonium hydroxide (TMAH), 800 ml of isopropyl alcohol (IPA), and 2.0 g of water were added, followed by a dropping funnel. 39.7 g of phenyltrimethoxydecane and 34.1 g of methyltrimethoxyanthracene were prepared. A mixed solution of an alkane and 7.6 g of tetramethoxynonane. The mixed solution was dropped into the flask at 10 ° C, and stirred at the same temperature for 3 hours, and then neutralized by adding a 10% aqueous HCl solution. 400 ml of toluene and 100 ml of water were added to the neutralized liquid to separate into two layers, and the obtained organic layer was concentrated under reduced pressure to remove the solvent, so that the solid concentration became 40 weight. The propylene glycol monomethyl ether acetate (PGMEA) was added as a % to adjust.

When the molecular weight (in terms of polystyrene) of the obtained polyoxyalkylene was measured by GPC, the weight average molecular weight (hereinafter abbreviated as "Mw") = 2,200. Further, the obtained resin solution was applied onto a ruthenium wafer by a spin coater so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured after prebaking (hereinafter referred to as "ADR" is 490Å/sec.

<Synthesis Example 2 (Synthesis of Polyoxyalkylene (Ia-2): Synthesis of Acid Catalyst)>

In a 2 L flask equipped with a stirrer, a thermometer, and a cooling tube, 1.6 g of a 35% aqueous hydrochloric acid solution, 300 ml of PGMEA, and 27.4 g of water were added, and then 49.6 g of phenyltrimethoxydecane and 34.1 g were prepared in a dropping funnel. A mixed solution of methyltrimethoxydecane. The mixed solution was dropped into a flask at 10 ° C, and stirred at the same temperature for 10 hours. Then, 200 ml of toluene and 100 ml of water were added to the reaction mixture to separate into two layers, and the obtained organic layer was The mixture was concentrated under reduced pressure, and the solvent was removed, and PGMEA was added to the concentrate to adjust the concentration of the solid component to 40% by weight. When the molecular weight of the obtained polyoxyalkylene (in terms of polystyrene) and the ADR in a 5% TMAH aqueous solution were measured in the same manner as in Synthesis Example 1, Mw = 1,330, at 5% TMAH. The ADR in the aqueous solution is 160 Å/sec.

<Synthesis Example 3 (Synthesis of Polyoxyalkylene (Ib-1): Acid Catalyst Synthesis)>

The polysiloxane was synthesized in the same manner as in Synthesis Example 2 except that the stirring time was changed to 3 hours after the mixed solution of phenyltrimethoxydecane and methyltrimethoxydecane was added thereto. When the molecular weight of the obtained polyoxynitane (in terms of polystyrene) was measured in the same manner as in Synthesis Example 1, Mw was 1,780. Further, the obtained resin solution was applied onto a tantalum wafer by a spin coater so that the film thickness after prebaking was 2 μm, and the ADR in a 2.38% TMAH aqueous solution was measured after prebaking. , 11,100 Å / sec.

<Synthesis Example 4 (Synthesis of Polyoxyalkylene (Ib-2): Acid Catalyst Synthesis)>

Instead of using 49.7 g of phenyltrimethoxydecane, 34.1 g of methyltrimethoxynonane and 7.6 g of tetramethoxynonane, 49.6 g of phenyltrimethoxydecane and 34.1 g of methyltrimethyl are used. A polydecane gas was synthesized in the same manner as in Synthesis Example 2 except that the mixed solution of oxydecane was changed to a stirring time of 3 hours. The molecular weight of the obtained polyoxyxane (in terms of polystyrene), the ADR in the 2.38% TMAH aqueous solution, Mw = 1,590, and the ADR in the 2.38% TMAH aqueous solution was 9,530 in the same manner as in Synthesis Example 3. Å/sec.

<Synthesis Example 5 (Synthesis of Polyoxyalkylene (Ib-3): Synthesis of Base Catalyst)>

In the same manner as in Synthesis Example 1, 54.7 g of a 25% aqueous solution of TMAH and 800 ml of IPA were added, followed by preparation of 39.7 g of phenyltrimethoxydecane, 34.1 g of methyltrimethoxydecane and 7.6 in a dropping funnel. a mixed solution of g tetramethoxy decane. The mixed solution was dropped into the flask at 10 ° C, and after stirring at the same temperature for 3 hours, 10% HCl was added. The aqueous solution is neutralized. 400 ml of toluene and 100 ml of water were added to the neutralized liquid to separate into two layers, and the obtained organic layer was concentrated under reduced pressure to remove the solvent, and then in the concentrate to make the concentration of the solid component. PGMEA was added to adjust to 40% by weight. The molecular weight of the obtained polyoxyalkylene (in terms of polystyrene), the ADR in the 2.38% TMAH aqueous solution, Mw = 1,720, and the ADR in the 2.38% TMAH aqueous solution was 4,850 in the same manner as in Synthesis Example 3. Å/sec.

<Synthesis Example 6 (Synthesis of Polyoxyalkylene (Ic-1): Synthesis of Acid Catalyst)>

Instead of using 49.7 g of phenyltrimethoxydecane, 34.1 g of methyltrimethoxydecane and 15.2 g of tetramethoxynonane, 49.6 g of phenyltrimethoxydecane and 34.1 g of methyltrimethyl were used. A polydecane was synthesized in the same manner as in Synthesis Example 3 except that the mixed solution of oxydecane was changed to a stirring time of 6 hours. The molecular weight of the obtained polyoxyxane (in terms of polystyrene), the ADR in the 2.38% TMAH aqueous solution, Mw = 2,040, and the ADR in the 2.38% TMAH aqueous solution was 1,100 in the same manner as in Synthesis Example 3. Å/sec.

<Synthesis Example 7 (Synthesis of Polyoxyalkylene (Ic-2): Acid Catalyst Synthesis)>

The polysiloxane was synthesized in the same manner as in Synthesis Example 3 except that the stirring time after the dropwise addition of the mixed solution of phenyltrimethoxydecane and methyltrimethoxydecane was changed to 8 hours. The molecular weight of the obtained polyoxyxane (in terms of polystyrene), the ADR in a 2.38% TMAH aqueous solution, Mw = 1,510, and the ADR in the 2.38% TMAH aqueous solution was 390 Å in the same manner as in Synthesis Example 3. /second.

<Synthesis Example 8 (Synthesis of Polyoxyalkylene (Ic-3): Acid Catalyst Synthesis)>

Synthesis of polydecane oxide in the same manner as in Synthesis Example 4 except that the stirring time after the dropwise addition of a mixed solution of phenyltrimethoxydecane, methyltrimethoxynonane and tetramethoxynonane was changed to 5 hours. . The molecular weight of the obtained polyoxyxane (in terms of polystyrene) and the ADR in a 2.38% TMAH aqueous solution were measured in the same manner as in Synthesis Example 4, and Mw was 1,890, and the ADR in the 2.38% TMAH aqueous solution was 2,440 Å / sec.

<Synthesis Example 9 (Synthesis of Polyoxane of Comparative Example 1 : Synthesis of Base Catalyst)>

Instead of using 39.6 g of phenyltrimethoxydecane, 34.1 g of methyltrimethoxydecane and 7.6 g of the tetra-ethylene, a mixed solution of 49.6 g of phenyltrimethoxydecane and 34.1 g of methyltrimethoxydecane was used. The mixed solution of oxydecane was synthesized in the same manner as in Synthesis Example 1 except that the amount of water added to the flask was changed to 1.0 g. The molecular weight of the obtained polyoxyxane (in terms of polystyrene), the ADR in the 2.38% TMAH aqueous solution, Mw = 1,520, and the ADR in the 2.38% TMAH aqueous solution were 150 Å in the same manner as in Synthesis Example 3. /second.

<Synthesis Example 10 (Synthesis of Polyoxane of Comparative Example 2: Acid Catalyst Synthesis)>

The polysiloxane was synthesized in the same manner as in Synthesis Example 3 except that the stirring time after the dropwise addition of the mixed solution of phenyltrimethoxydecane and methyltrimethoxydecane was changed to 10 hours. The molecular weight of the obtained polyoxyxane (in terms of polystyrene), the ADR in the 2.38% TMAH aqueous solution, Mw = 1,730, and the ADR in the 2.38% TMAH aqueous solution was 160 Å in the same manner as in Synthesis Example 3. /second.

<Synthesis Example 11 (Synthesis of Polyoxane of Comparative Table 3: Acid Catalyst Synthesis)>

The polysiloxane was synthesized in the same manner as in Synthesis Example 3 except that the stirring time after the dropwise addition of the mixed solution of phenyltrimethoxydecane and methyltrimethoxydecane was changed to 5 hours. The molecular weight of the obtained polyoxyxane (in terms of polystyrene), the ADR in the 2.38% TMAH aqueous solution, Mw = 1,790, and the ADR in the 2.38% TMAH aqueous solution was 3,500 in the same manner as in Synthesis Example 3. Å/sec.

In the following Table 1, the raw materials, the reaction catalyst, and the Mw and ADR of the obtained polyoxyalkylene are described for the synthesis examples.

<Example 1 (Positive photosensitive siloxane composition)>

Polyoxazane after mixing in a ratio of polyoxane (Ia-1): (Ib-1): (Ic-1) = (40% by weight): (30% by weight): (30% by weight) The mixture was adjusted to a PGMEA solution with a concentration of 35% and added to the equivalent of poly 12% by weight of 4-4'-(1-(4-(1-(4-hydroxyphenol)-1-methylethyl)phenyl)ethylidene) bisphenol of 2.0% oxime A compound modified by a naphthoquinone (hereinafter abbreviated as "PAC"). Further, KF-53 manufactured by Shin-Etsu Chemical Co., Ltd., which is 0.3% by weight of polysiloxane, was added as a surfactant to obtain a photosensitive siloxane composition.

The photosensitive siloxane composition was applied onto a ruthenium wafer by a spin coater, and after coating, it was prebaked on a hot plate at 100 ° C to adjust the film thickness to 2 μm. After prebaking, exposure was carried out at 180 mJ/cm ² using a Nikon FX-604 (NA = 0.1) g, h-ray exposure machine, and after washing with a 2.38% TMAH aqueous solution, washing with pure water was carried out. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off. Fig. 1 shows an SEM photograph of a line and space (L/S) pattern, and Fig. 2 shows an SEM photograph of a contact hole (C/H) pattern.

<Example 2 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-2): (Ic-1) = (40% by weight): (30% by weight): (30% by weight), in addition to In the same manner as in Example 1, a photosensitive decane composition was obtained, which was coated, exposed, developed, and washed. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Example 3 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-3): (Ic-1) = (40% by weight): (30% by weight): (30% by weight), and at 220 mJ/ A photosensitive decane composition was obtained in the same manner as in Example 1 except that exposure was carried out in cm ² , followed by coating, exposure, development, and washing. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Example 4 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-3): (Ic-2) = (40% by weight): (30% by weight): (30% by weight), and at 220 mJ/ A photosensitive decane composition was obtained in the same manner as in Example 1 except that exposure was carried out in cm ² , followed by coating, exposure, development, and washing. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Example 5 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-3): (Ic-3) = (40% by weight): (35 wt%): (25 wt%), and at 190 mJ A photosensitive decane composition was obtained in the same manner as in Example 1 except that exposure was carried out in /cm ² , and coating, exposure, development, and washing were carried out. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Example 6 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-2): (Ib-2): (Ic-2) = (35 wt%): (45 wt%): (20 wt%), and In the same manner as in Example 1, a photosensitive decane composition was obtained, which was coated, exposed, developed, and washed. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Example 7 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-2): (Ib-2): (Ic-1) = (35 wt%): (40 wt%): (25 wt%), in addition to In the same manner as in Example 1, a photosensitive decane composition was obtained, which was coated, exposed, developed, and washed. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Example 8 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-2): (Ib-2): (Ic-3) = (35 wt%): (35 wt%): (30 wt%), and In the same manner as in Example 1, a photosensitive decane composition was obtained, which was coated, exposed, developed, and washed. Then, by SEM observation, it was confirmed that the line and space (L/S) pattern and the contact hole (C/H) pattern of 5 μm were not peeled off.

<Comparative Example 1 (positive type photosensitive siloxane composition)>

The same procedure as in Example 1 except that the ratio of polyoxyalkylene was adjusted to (Ia-1): (Ib-2) = (65% by weight): (35 wt%) and exposure was performed at 130 mJ/cm ² . In this manner, a photosensitive decane composition is obtained and coated, exposed, developed, and washed. Then, SEM observation was carried out, and in terms of the resolution of either of 10 μm and 5 μm, development residues were confirmed for both the line and space (L/S) and contact hole (C/H) patterns. In particular, in the C/H pattern of 5 μm, the insoluble layer remained entirely. Figure 3 shows an SEM photograph of a 5 μm contact hole (C/H) pattern.

<Comparative Example 2 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-2): (Comparative 1) = (42% by weight): (28% by weight): (30% by weight), and at 130 mJ/cm ⁽² ) In the same manner as in Example 1, a photosensitive decane composition was obtained, and coating, exposure, development, and washing were carried out in the same manner as in Example 1. Then, SEM observation was carried out, and a developmental residue was confirmed for a 5 μm contact hole (C/H) pattern.

<Comparative Example 3 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-2): (Comparative 2) = (42% by weight): (28% by weight): (30% by weight), and at 130 mJ/cm ⁽² ) In the same manner as in Example 1, a photosensitive decane composition was obtained, and coating, exposure, development, and washing were carried out in the same manner as in Example 1. Then, SEM observation was carried out, and a developmental residue was confirmed for a 5 μm contact hole (C/H) pattern. Figure 4 shows an SEM photograph of a 5 μm contact hole (C/H) pattern.

<Comparative Example 4 (positive type photosensitive siloxane composition)>

The same procedure as in Example 1 was carried out except that the ratio of polyoxyalkylene was adjusted to (Ib-2): (Comparative 1) = (35 wt%): (65 wt%) and exposure was performed at 150 mJ/cm ² . In the manner, a photosensitive decane composition is obtained and coated, exposed, developed, and washed. Then, SEM observation was carried out, and a developmental residue was confirmed for a contact hole (C/H) pattern of 10 μm.

<Comparative Example 5 (positive type photosensitive siloxane composition)>

In addition to adjusting the ratio of polyoxyalkylene to (Ia-1): (Ib-2): (Comparative 3) = (35 wt%): (35 wt%): (30 wt%), and at 160 mJ/cm ⁽² ) In the same manner as in Example 1, a photosensitive decane composition was obtained, and coating, exposure, development, and washing were carried out in the same manner as in Example 1. Then, SEM observation was carried out, and for a contact hole (C/H) pattern of 5 μm, it was confirmed that there was a development residue in a deep recess in the peripheral portion of the hole.

The positive photosensitive siloxane compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were combined and shown in Table 2.

[Fig. 1] Fig. 1 is a SEM of a line-and-pitch (L/S) pattern of 5 μm after positive image formation with a 2.38% TMAH aqueous solution obtained in Example 1. photo.

[Fig. 2] Fig. 2 is a positive photosensitive siloxane composition obtained in Example 1, after being imaged with a 2.38% TMAH aqueous solution, 5 μm SEM photograph of the contact hole (C/H) pattern.

[Fig. 3] Fig. 3 is a SEM photograph of a 5 μm contact hole (C/H) pattern of a positive photosensitive siloxane composition obtained in Comparative Example 1 after development with a 2.38% TMAH aqueous solution. .

[Fig. 4] Fig. 4 is a SEM photograph of a 5 μm contact hole (C/H) pattern of a positive photosensitive siloxane composition obtained in Comparative Example 3 after development with a 2.38% TMAH aqueous solution. .

Claims (9)

A positive photosensitive siloxane composition comprising (I) a polyoxy siloxane, a (II) diazonaphthoquinone derivative, and a (III) solvent positive photosensitive siloxane composition, wherein The polyoxyalkylene (I) includes at least one of the following polyoxyalkylene oxides (Ia), at least one of the following polyoxyalkylene oxides (Ib), and at least one of the following polyoxyalkylene oxides (Ic). (A) Polyoxane (Ia) is obtained by hydrolyzing and condensing a decane compound represented by the formula (1) in the presence of an acidic or basic catalyst, and the film after prebaking is at 5 wt% of NaOH. ammonium-based aqueous soluble, the dissolution rate of less 1,000Å / sec poly silicon oxide _{^{alkyl; R 1 n Si (OR 2}} ) 4-n ( wherein, R ¹ represents a methylene group at any of the available oxygen replacing a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms and optionally hydrogen replaced with fluorine; n is 0 or 1; R ² represents a carbon number of 1~ (B) a polyoxyalkylene (Ib) obtained by hydrolyzing and condensing a decane compound of the formula (1) in the presence of an acidic or basic catalyst, and the film after prebaking is at 2.38 weight. Polyoxane having a dissolution rate of 4,000 Å/sec or more in an aqueous solution of tetramethylammonium hydroxide; (C) The polydecane (Ic) is obtained by hydrolyzing and condensing the decane compound of the formula (1) in the presence of an acidic or basic catalyst, and the pre-baked film is in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. The polyoxane having a dissolution rate of 200 Å/sec or more and 3000 Å/sec or less. The positive photosensitive siloxane composition according to the first aspect of the invention, wherein the polyoxy siloxane (Ia) is obtained by hydrolyzing and condensing the decane compound in the presence of a basic catalyst. The positive photosensitive decane composition according to claim 1 or 2, wherein the total weight of the polyoxyalkylene (Ia) and (Ib) and the weight ratio of the polyoxyalkylene (Ic) are From 95/5 to 50/50. The positive photosensitive siloxane composition according to any one of claims 1 to 3, wherein the weight ratio of the polyoxyalkylene (Ia) to (Ib) is from 30/70 to 70/30. The positive photosensitive siloxane composition according to any one of claims 1 to 4, wherein the polyoxy siloxane (I) contains 5 mole% to 30 mole% of a decane compound, the decane compound Among the decane compounds of the formula (1) constituting the polyoxyalkylene, n = 0. The positive photosensitive siloxane composition according to any one of claims 1 to 5, wherein at least one of the polyoxyalkylenes (Ia), (Ib) and (Ic) Among the decane compounds of the formula (1) constituting these polyoxyalkylene oxides, the decane compound represented by the methyl group of R ¹ is an average of 20 mol% to 80 mol%. A positive photosensitive decane composition according to claim 6 of the patent application, wherein, in the polyoxane (I), among the decane compounds of the formula (1) constituting the polyoxyalkylene, R ^The average decane compound represented by ¹ methyl group accounts for 20 mol% to 80 mol%. A cured film which is according to any one of claims 1 to 7 of the patent application scope Formed by a positive photosensitive siloxane composition. An element having a cured film as in item 8 of the patent application.